CN110898819A - Magnetic porous nano-particles - Google Patents

Magnetic porous nano-particles Download PDF

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CN110898819A
CN110898819A CN201911250566.9A CN201911250566A CN110898819A CN 110898819 A CN110898819 A CN 110898819A CN 201911250566 A CN201911250566 A CN 201911250566A CN 110898819 A CN110898819 A CN 110898819A
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magnetic
particles
shell
polydopamine
nanoparticle
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阎斌
林佳友
吴江
向淋
王桂华
陈�胜
顾迎春
南昼
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Sichuan University
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Sichuan University
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Abstract

The invention provides a magnetic porous nanoparticle which takes polydopamine with a porous structure as a shell and has magnetic particles with the size of 4 nm-6 nm in the shell and/or pores of the shell. The magnetic porous nano-particles have higher adsorption efficiency on organic dyes due to the shell structure and the physicochemical property, and show better removal capability on the organic dyes by matching with the high-efficiency degradation efficiency of the magnetic particles on the organic dyes and the reduction capability of the polydopamine shell on the magnetic particles after reaction. The invention also provides a preparation method, a use method and a regeneration method of the magnetic porous nano-particles.

Description

Magnetic porous nano-particles
Technical Field
The invention relates to the technical field of organic polymers and application thereof, in particular to magnetic porous nanoparticles and preparation and regeneration methods and application thereof.
Background
In recent years, with the rapid development of textile industry in China, organic dyes are widely applied due to the characteristics of bright color, firm coloring, difficult degradation and the like. However, due to the chemical stability and the difficult biodegradability of the organic dye, the organic dye wastewater is difficult to be treated by the traditional physical method, chemical method or biochemical method, becomes one of the main harmful industrial wastewater, and poses great threat to the safety of human body and environment.
In order to solve the problems, the Chinese invention patent CN2009102642242 discloses a method for rapidly degrading organic dye wastewater, which adopts sodium bismuthate to degrade triphenylmethane dye wastewater; chinese invention patent application CN2017110456758 discloses a method for photocatalytic degradation of anthraquinone organic dye-containing wastewater, and prepared Cu is adopted2O/graphene/α -Fe2O3The nanotube array composite photocatalytically degrades the waste water containing anthraquinone organic dye. The technical scheme only aims at certain dye wastewater, so that the problem of narrow application range exists. The Chinese patent application CN2019105678574 discloses a method for treating organic dye in wastewater, wherein photocatalyst modified graphene composite sponge is adopted to carry out adsorption and degradation treatment on the organic dye in the wastewater. In the above technical scheme, although the type of the organic dye is not limited, the organic dye has limited processing capacity, so as to achieve the purposeThe treatment effect is that the material has to be replaced; and the degradation treatment of the material also depends on exposure to light, so that the material is not easy to implement.
At present, the method for degrading and treating organic matters by using high-activity hydroxyl free radicals (. OH) through the advanced oxidation of a Fenton system is used for treating organic dye wastewater due to the characteristics of low cost, excellent treatment effect, simple operation and the like. The existing Fenton reagent for treating organic pollutants mainly comprises zero-valent iron, iron-based clay, silicon dioxide, zeolite, iron-based materials and iron oxide-based materials. And is made of ferroferric oxide (Fe)3O4) The iron oxide-based material as the representative is considered to be an ideal Fenton reagent because of its characteristics of effectively degrading organic compounds and being easily separated. However, the prior art scheme is restricted by the valence state and degradation performance of ferroferric oxide, so that the application of the ferroferric oxide is limited to a narrow pH value range.
Disclosure of Invention
One of the objects of the present invention is to provide a magnetic porous nanoparticle.
The magnetic porous nano-particle has a polydopamine closed shell with a porous structure, and magnetic particles are arranged in the polydopamine closed shell.
The magnetic porous nano-particle can also simultaneously have magnetic particles in the shell and the pores of the shell of polydopamine with a porous structure.
The magnetic porous nano-particle has a polydopamine shell with the aperture of 5-10 nm and the specific surface area of 190m2/g～210m2/g。
The magnetic particle size of the magnetic porous nano-particle is 4 nm-6 nm.
The magnetic particles of the magnetic porous nano particles are ferroferric oxide particles.
The magnetic particles in the polydopamine shell of the magnetic porous nano-particle are independently or in cluster distribution, and gaps are reserved among the particles or clusters.
The polydopamine shell of the magnetic porous nanoparticle has an irregular shape.
The shape and the internal structure of the magnetic porous nano-particles are similar to those of pomegranate.
The magnetic porous nano-particle has chemical stability within the range of pH value of 2-10 due to the pH affinity of the polydopamine shell.
The method for preparing the magnetic porous nano-particles comprises the following steps:
s1, preparing magnetic particles, preferably preparing ferroferric oxide particles with the particle size of 4 nm-6 nm by a solvent method (such as the ACS Nano,2011,5, 6315);
s2, mixing the ferroferric oxide particles prepared in the step S1 and tetraethyl orthosilicate in a mass ratio of 1: 1-1: 3 in a stober alkaline environment (such as a Colloid Interface Sci.,1968,26, 62-69), and stirring for not less than 24 hours to obtain a silicon dioxide-magnetic particle compound solution;
s3, weighing dopamine according to the proportion of 0.5-1 based on the mass of the ferroferric oxide particles in the step S2, adding the dopamine into the compound solution in the step S2, and stirring for not less than 24 hours;
s4, centrifugally treating the reaction liquid obtained in the step S3, putting the collected solid product into HCl-tris buffer solution with the same volume as that in the step S2, and carrying out hydrothermal treatment at 140-160 ℃ for not less than 24 h;
and S5, collecting the product subjected to the hydrothermal treatment in the step S4, and washing the product by using ethanol and deionized water until the supernatant is colorless and transparent.
By adjusting the mass ratio of tetraethyl orthosilicate to ferroferric oxide particles in the method, the magnetic porous nanoparticles with different ferroferric oxide particle contents can be obtained.
According to the content of the ferroferric oxide particles, the dosage of dopamine can be predicted, and then a polydopamine shell with a proper thickness can be obtained by adjusting the mass ratio of the dopamine to the ferroferric oxide particles in the method, so that the magnetic porous nanoparticles have better performance.
In the above method, the dosage ratio of the ferroferric oxide particles to tetraethyl orthosilicate, the dosage ratio of dopamine to the ferroferric oxide particles, the hydrothermal treatment temperature and the like all affect the appearance and performance of the final product (see attached tables 1-3 for details).
The invention also aims to provide a method for degrading and treating various organic dyes.
The method for degrading and treating various organic dyes is realized by the magnetic porous nano-particles provided by the invention.
Magnetic particles (hereinafter, referred to as ferroferric oxide particles for example) in the magnetic porous nanoparticles are subjected to a degradation function by reducing hydrogen peroxide to generate hydroxyl radicals (detailed in a reaction formula 1) to react with organic pollutants (organic dyes) (detailed in a reaction formula 2).
Fe2+(Fe3O4)+H2O2＝Fe3++·OH+OH-(reaction formula 1)
OH + OPs (organic pollutants) ═ CO2+H2O (reaction type 2)
When the ferroferric oxide is used alone for Fenton reaction, the pH value of a liquid phase system needs to be strictly regulated and controlled to maintain acidity, so that hydroxide ions generated in the reaction formula 1 are prevented from being combined with ferric ions to form ferric hydroxide precipitates.
In the magnetic porous nano-particles provided by the invention, a large number of ferroferric oxide particles are positioned in a polydopamine shell. On one hand, the polydopamine shell has good adsorption and energy absorption on organic pollutants within the pH range of 2-10, the adsorbed organic pollutants can be conveyed into the shell through the porous structure of the polydopamine shell, and quickly permeate into gaps among ferroferric oxide particles to react with hydroxyl radicals generated by the action of the ferroferric oxide particles and hydrogen peroxide, so that the organic pollutants are quickly degraded; on the other hand, the catechol structure contained in dopamine in the polydopamine shell can utilize the reducibility thereof to convert Fe produced in reaction formula 1 into Fe3+Is reduced to Fe again2+The formation of ferric hydroxide precipitate is avoided, the treatment efficiency of ferroferric oxide particles on organic pollutants is enhanced, and meanwhile, the structural stability of the magnetic porous nano particles is kept.
The magnetic porous nano particles adopt ferroferric oxide particles with the particle size of only 4nm to 6nm, the distribution of the ferroferric oxide particles in the polydopamine shell is irregular and has independent, agglomerated and clustered distribution, so that irregular gaps are formed in the shell, the polydopamine shell further has a pomegranate-like appearance structure, and compared with the spherical shell which is formed by adopting magnetic particles with the particle size of more than 100nm and regularly distributed in the prior art, the magnetic porous nano particles have a larger specific surface. The increased specific surface area of the pomegranate-shaped polydopamine shell is matched with the porous structure of the pomegranate-shaped polydopamine shell, so that the adsorption efficiency of the magnetic nanoparticles on organic dyes is greatly improved. As shown in the foregoing, when the ferroferric oxide particles with the particle size of only 4nm to 6nm in the magnetic porous nanoparticles react with hydrogen peroxide, a large amount of hydroxyl radicals are more easily generated, so that the magnetic porous nanoparticles have higher degradation efficiency on organic dyes. When the polydopamine shell adsorbs organic pollutants into the polydopamine shell, the ferroferric oxide particles react with hydrogen peroxide to generate a large amount of hydroxyl free radicals, so that the organic pollutants contacted with the polydopamine shell can be rapidly degraded, and therefore, the magnetic nanoparticles can show extremely high treatment efficiency and excellent treatment effect on organic pollutants such as organic dyes.
The method for degrading and treating the organic dye by the magnetic porous nano particles comprises the following steps:
s1, based on the volume of the organic dye, according to the mass-to-volume ratio of 1:104～1:106Weighing the magnetic porous nano-particles provided by the invention;
s2, adjusting the pH of the mixed liquid obtained in the step S1 to be neutral, and shaking for 10-60 min at normal temperature.
The magnetic porous nano-particles in the method can adopt various forms such as liquid dispersion or powder and the like, and the content of the magnetic porous nano-particles in the forms is taken as a weighing basis.
The mass-to-volume ratio of the magnetic porous nanoparticles to the organic dye in the above method is determined by the concentration of the organic dye.
As described above, since the present invention can provide magnetic porous nanoparticles having different contents of the fine particles of ferroferric oxide, magnetic porous nanoparticles having different contents of the fine particles of ferroferric oxide can be used according to the concentration of the organic dye.
The organic dye in the method comprises but is not limited to methylene blue, rhodamine B, Congo red and neutral red, and the components can be singly present or be present in a mixed mode.
The invention also aims to provide a material capable of degrading and processing various organic dyes.
The material may be in liquid dispersion or any solid form.
The ability of the material to degrade various organic dyes results from the magnetic porous nanoparticles provided by the present invention.
The degradation efficiency of the material to organic dye is directly related to the content of the magnetic porous nano particles.
The material has the capacity of multiple recycling, and the capacity is realized by performing regeneration treatment on the magnetic porous nano particles.
As mentioned above, the particle size of the ferroferric oxide particles in the magnetic porous nano particles provided by the invention is only 4-6 nm. The particle size is remarkably reduced, the degradation efficiency is improved, and simultaneously, the reaction efficiency of the magnetic porous nano-particles and a catechol structure of dopamine serving as a polydopamine shell component is also improved, so that the stability of the material is improved, and compared with the existing material adopting the magnetic particles with the particle size of over 100nm, the magnetic porous nano-particles have lower leaching rate, and have better recycling capability.
The regeneration method of the magnetic porous nano-particles provided by the invention comprises the following steps:
s1, in the organic dye solution subjected to degradation treatment, magnetic porous nano particles are enriched and separated by utilizing magnetism;
s2, putting the magnetic porous nano-particles separated in the step S1 into an absolute ethyl alcohol and deionized water solution which are configured in an equal volume, and performing immersion washing for multiple times until an eluate is colorless.
The magnetism in the method can adopt various tangible or intangible magnetic forces such as a magnet, a magnetic bead, a magnetic field and the like.
The method can separate the magnetic porous nanoparticles by utilizing magnetic enrichment, and is realized by superparamagnetism of the magnetic porous nanoparticles provided by the invention.
The polydopamine shell of the magnetic porous nano-particle provided by the invention has a porous structure and a larger specific surface area, and is beneficial to quickly adsorbing organic dye; the small-particle ferroferric oxide particles in the shell or in the pores of the shell part can efficiently react with hydrogen peroxide, and the organic dye adsorbed by the shell is rapidly degraded. The two are matched with each other, so that the treatment effect and efficiency of the organic dye are obviously improved.
The magnetic porous nanoparticle provided by the invention has a wider pH application range due to the polydopamine shell, so that the magnetic porous nanoparticle or a material consisting of the magnetic porous nanoparticle can be used for treating cationic dyes and anionic dyes at the same time.
According to the magnetic porous nano-particles provided by the invention, the small-particle ferroferric oxide nano-particles are adopted, so that the material stability of the magnetic porous nano-particles is improved, and a smaller leaching rate and a better recycling capability are obtained.
According to the preparation method of the magnetic porous nano-particles, provided by the invention, the consumption of the rest raw materials can be accurately calculated according to the consumption of the ferroferric oxide nano-particles, so that the magnetic porous nano-particles with specific treatment efficiency can be accurately prepared according to actual needs (organic dye pollution conditions such as dye types and concentrations). It is advantageous to control the processing cost and the processing efficiency.
Drawings
In order to more clearly illustrate the present invention or the technical solutions in the prior art, the following will briefly describe the embodiments or drawings required for technical description, and obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a low power transmission electron micrograph of an organic polymer in example 1 of the present application.
FIG. 2 is a high-power transmission electron micrograph of an organic polymer in example 1 of the present application.
FIG. 3 is a graph showing adsorption and desorption of an organic polymer at 77K to nitrogen in example 1 of the present application.
FIG. 4 is a graph showing a distribution of pore diameters of an organic polymer in example 1 of the present application.
FIG. 5 is an X-ray diffraction chart of an organic polymer in example 1 of the present application.
FIG. 6 is a hysteresis chart of an organic polymer in example 1 of the present application.
FIG. 7 is a TEM image of an organic polymer in example 5 of the present application.
FIG. 8 is a graph showing the removal rate of the organic polymer at a concentration of 40mg/L methylene blue for different periods of time in example 6 of the present application.
FIG. 9 is a graph showing the removal rate of the organic polymer at 300mg/L methylene blue concentration for different time periods in example 7 of the present application.
FIG. 10 is a graph showing the removal rate of organic polymer at 80mg/L neutral red concentration for different time periods in example 8 of the present application.
FIG. 11 is a graph showing the removal rate of organic polymer at 80mg/L Congo red concentration for different time periods in example 9 of the present application.
FIG. 12 is a graph showing the removal rate of the organic polymer at 80mg/L methylene blue concentration at different pH values for different time periods in example 10 of the present application.
FIG. 13 is a graph showing the relationship between the number of times of recycling of the organic polymer and the removal rate of methylene blue in example 12 of the present application.
Detailed Description
In the following, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the claimed embodiments. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not as restrictive.
Preparation of
Example 1
Step 1, preparing magnetic Fe by adopting a solvent method3O4Nano-particles: FeCl is added3·6H2O、NaHCO3Adding vitamin C into a solution with a proper volume according to a mass ratio of 10:1:1, reacting for 1h, transferring into a hydrothermal kettle, performing hydrothermal treatment at 150 ℃ for 4h, and cleaning the product to obtain magnetic Fe with the particle size of 4-6 nm3O4Nano particles dispersed in deionized water for later use;
step 2, preparing a silicon dioxide-magnetic particle compound solution: mixing TEOS and the magnetic Fe prepared in the step 1 according to the mass ratio of 2:13O4Adding the nano particles into a mixed solution of 25% ammonia water, absolute ethyl alcohol and deionized water prepared according to a volume ratio of 1:20:80, and stirring for 24 hours;
step 3, preparing magnetic porous nano particles: weighing the magnetic Fe in the step 23O4D, putting the DA with the same mass as the nano particles into the silicon dioxide-magnetic particle compound solution prepared in the step 2, stirring for 24 hours and then centrifuging; putting the collected solid product into HCl-tris solution with the volume equal to that of the silicon dioxide-magnetic particle compound solution prepared in the step 2, performing hydrothermal treatment at 140 ℃ for 24 hours, and washing the product with ethanol and deionized water until the washing liquid is colorless and transparent.
The observation and analysis of the obtained product gave the following results:
as shown in FIG. 1, the scanning electron micrograph shows that the product particles are clear and irregular in shape.
As shown in FIG. 2, the TEM micrograph showed that the product had an irregularly shaped shell, magnetic Fe3O4The nanoparticles are mostly distributed inside the shell.
As shown in FIG. 3, the nitrogen adsorption and desorption curve of the product at 77K has a remarkable and wide hysteresis region, which belongs to a typical isothermal adsorption type IV line, and the product is shown to have a mesoporous structure. By calculation, the specific surface area thereof was found to be 200m2/g。
As shown in fig. 4, further analyzing the pore size information corresponding to the curve in fig. 3, it can be seen that the pore size of the product is mainly distributed in 8nm and belongs to a pore channel structure mainly containing mesopores.
As shown in fig. 5, the X-ray diffraction pattern showed that the product had distinct magnetic cubic phase (JCPDS No.89-0688) and an amorphous diffraction peak (2 θ ═ 26 °) typically caused by polydopamine polymer.
As shown in fig. 6, the superconducting quantum interference hysteresis loop shows that the saturation magnetization value of the product does not have any coercive force and remanence, indicating that the product has superparamagnetic behavior.
Example 2
Step 1. preparing magnetic Fe with grain size of 4-6 nm by any method3O4A nanoparticle;
step 2, preparing a silicon dioxide-magnetic particle compound solution: mixing TEOS and the magnetic Fe prepared in the step 1 according to the mass ratio of 2.5:13O4Nano particles are put into any solution meeting the Stober alkaline environment requirement and stirred for not less than 24 hours;
step 3, weighing 0.5 times of the magnetic Fe in the step 23O4D, adding DA in the mass of the nano particles into the compound solution obtained in the step 2, stirring for not less than 24 hours, and centrifuging; putting the collected solid product into HCl-tris solution with the volume equal to that of the silicon dioxide-magnetic particle compound solution prepared in the step 2, carrying out hydrothermal treatment at 140 ℃ for not less than 24 hours, and washing the product with ethanol and deionized water until the washing liquid is colorless and transparent.
The specific surface area of the obtained product is 190m calculated by a nitrogen adsorption and desorption curve at 77K2The pore diameter is intensively distributed at 7 nm.
Example 3
Step 1, screening to obtain magnetic Fe with the grain diameter of 4 nm-6 nm3O4A nanoparticle;
step 2, preparing a silicon dioxide-magnetic particle compound solution: mixing TEOS and the magnetic Fe prepared in the step 1 according to the mass ratio of 3:13O4Nano particles are put into any solution meeting the Stober alkaline environment requirement and stirred for not less than 24 hours;
step 3, weighing 0.8 times of the magnetic Fe in the step 23O4D, adding DA in the mass of the nano particles into the compound solution obtained in the step 2, stirring for not less than 24 hours, and centrifuging; putting the collected solid product into the silica-magnetic particle composite solution prepared in the step 2Carrying out hydrothermal treatment at 150 ℃ for not less than 24h in HCl-tris solution with equal liquid volume, and washing the product with ethanol and deionized water until the washing liquid is colorless and transparent.
The specific surface area of the obtained product is 210m calculated by a nitrogen adsorption and desorption curve at 77K2The pore diameter is intensively distributed at 8 nm.
Example 4
Step 1, magnetic Fe with the grain diameter of 4 nm-6 nm is purchased3O4A nanoparticle;
step 2, preparing a silicon dioxide-magnetic particle compound solution: mixing TEOS and the magnetic Fe prepared in the step 1 according to the mass ratio of 2:13O4Nano particles are put into any solution meeting the Stober alkaline environment requirement and stirred for not less than 24 hours;
step 3, weighing 0.8 times of the magnetic Fe in the step 23O4D, adding DA in the mass of the nano particles into the compound solution obtained in the step 2, stirring for not less than 24 hours, and centrifuging; putting the collected solid product into HCl-tris solution with the volume equal to that of the silicon dioxide-magnetic particle compound solution prepared in the step 2, carrying out hydrothermal treatment at 160 ℃ for not less than 24 hours, and washing the product with ethanol and deionized water until the washing liquid is colorless and transparent.
The specific surface area of the obtained product is 201m calculated by a nitrogen adsorption and desorption curve at 77K2The pore diameter is intensively distributed at 8 nm.
Example 5
It differs from example 1 in that the hydrothermal temperature in step 3 was 120 ℃.
As shown in fig. 7, the tem photograph shows that a relatively large amount of silica still remains in the particles, making the outer shell thereof relatively round and smooth, and it is difficult to observe the presence of pores in the outer shell. Further, the specific surface area of the product is only 50m by calculation2(iv)/g, and no mesoporous structure.
Removal of organic dyes
In the following examples, the magnetic porous nanoparticles provided by the present invention were used to treat cationic dyes represented by the common dyes methylene blue and neutral red, and anionic dyes represented by the common dye congo red.
Example 6
Based on the volume of the methylene blue solution to be treated with the concentration of 40mg/L, according to the volume-to-mass ratio of 1041 weighing the magnetic porous nano-particles prepared in the embodiment 1, adding a proper amount of hydrogen peroxide solution with the concentration of 30 percent, mixing, adjusting the pH value to be neutral, and oscillating the mixed solution. And respectively taking reaction liquid after shaking treatment for 5min, 10min, 15min, 25min, 40min and 60min, filtering, and measuring the concentration of the residual methylene blue solution by using a visible spectrophotometer.
As shown in fig. 8, at the 5 th min after the shaking treatment, the removal rate of methylene blue in the solution reaches 90%; at 10min, the removal rate reaches the peak value; the removal rate is kept stable between the 10 th min and the 60 th min. Therefore, the magnetic porous nano-particles have extremely high removal efficiency on methylene blue solution with the concentration of 40 mg/L.
The magnetic porous nano particles are adsorbed by a porous polydopamine shell, and the magnetic Fe3O4The reaction treatment mode of the nano particles degrades and removes methylene blue, so compared with the existing method which only depends on adsorption treatment of organic dye, the method has better stability and does not need subsequent treatment.
Example 7
It differs from example 6 in that the concentration of the methylene blue solution to be treated was 300 mg/L.
As shown in fig. 9, the removal rate of methylene blue in the solution reached 50% at the 5 th min after the shaking treatment, and then the removal rate of methylene blue was continuously increased with time until the removal rate of methylene blue was more than 80% at the 60 th min. Therefore, the magnetic porous nano-particles have high removal efficiency even in the process of treating methylene blue solution with extremely high concentration. According to calculation, the explanation amount of the magnetic porous nano-particles to methylene blue is 2600mg/g at 60 min.
Methylene blue molecules which are absorbed by the shell and enter the shell are firstly well dispersed with magnetic Fe in the shell3O4The hydroxyl free radicals generated by the reaction of the nano-particles and the hydrogen peroxide are rapidly reacted and removed, so that the magnetic porous nano-particles in the early stage have extremely high removal efficiency on methylene blue. With the continuous entry of methylene blue molecules, the methylene blue molecules and magnetic Fe in the shell3O4The contact probability of the nano particles is reduced, the content of hydroxyl free radicals is reduced, although the magnetic particles can be reduced to restore Fe through a polydopamine shell after methylene blue is degraded and treated2+However, the reduction process still requires a certain time, so after the 5 th min of the shaking treatment, the removal efficiency of the magnetic porous nanoparticles to the methylene blue is reduced compared with the former stage, but the removal efficiency still keeps a stable and continuously improved trend.
In practical application, aiming at the water body polluted by high-concentration organic dye, the magnetic porous nano-particles with high content of ferroferric oxide particles can be prepared by adjusting the mass ratio of tetraethyl orthosilicate to ferroferric oxide particles, so as to obtain better methylene blue removal rate.
Example 8
It differs from example 6 in that a neutral red solution of a cationic dye having a concentration of 80mg/L is to be treated.
As shown in fig. 10, at the 5 th min after the shaking treatment, the removal rate of neutral red in the solution is over 75%; at 15min, the removal rate is already close to the peak; at the time of 60min, the removal rate can reach 100 percent, and the removal amount reaches 800 mg/g.
Example 9
It differs from example 6 in that an anionic dye Congo red solution having a concentration of 80mg/L is to be treated.
As shown in fig. 11, at the 5 th min after the shaking treatment, the removal rate of neutral red in the solution is greater than 60%; at the 40min, the removal rate can reach 100 percent, and the removal amount reaches 800 mg/g.
It can be seen from the combination of example 8 and example 9 that the magnetic porous nanoparticle has strong removal capability for both cationic dyes and anionic dyes.
Example 10
Based on the volume of the organic dye solution to be treatedVolume to mass ratio of 1041 the magnetic porous nanoparticles prepared in example 1 were weighed. Preparing methylene blue solutions with pH values of 2, 4, 6, 8 and 10 and a concentration of 80mg/L respectively, putting the weighed magnetic porous nano-particles and a proper amount of hydrogen peroxide solution into the methylene blue solutions, mixing and oscillating. Taking each group of reaction liquid after shaking treatment for 5min, 10min, 15min, 25min, 40min and 60min, filtering, and measuring the concentration of the residual methylene blue solution by using a visible spectrophotometer.
As shown in fig. 12, although the range of pH span of the organic dye solution to be treated is large, the removal rate of the magnetic porous nanoparticles to methylene blue can reach over 90% at the 60 th min of oscillation, and most of the removal rates are 100%.
As can be seen from fig. 8 to 12, even when the organic dye solution having a relatively high concentration is treated with the magnetic porous nanoparticles of the present invention at a relatively low dose ratio, the organic dye removal rate of 50% or more can be obtained within 5min after the start of the treatment, and the organic dye removal rate of 90% or more can be obtained within 60min after the start of the treatment. Therefore, the magnetic porous nano-particles have extremely high degradation speed on organic dyes, and have the capability of realizing 90% degradation treatment effect in an extremely short time by increasing the adding ratio, increasing the content of magnetic particles in the particles and the like.
Recovery and regeneration
Example 11
The magnetic porous nanoparticles were enriched from the treated mixture solution of example 6 by using a magnet, separated and transferred to a washing apparatus.
And (3) washing the magnetic porous nano particles by adopting absolute ethyl alcohol and deionized water which are prepared in equal proportion until washing liquid is colorless and transparent, and completing the recovery and regeneration of the magnetic porous nano particles.
After the treatment, the particles can be enriched again by the magnet and transferred to deionized water for dispersion and standby.
Example 12
Step 1, using the volume of methylene blue solution to be treated and with the concentration of 80mg/LOn the basis of the volume mass ratio of 1041 weighing the magnetic porous nano-particles regenerated in the embodiment 11, adding a proper amount of hydrogen peroxide solution with the concentration of 30 percent, mixing, adjusting the pH value to be neutral, shaking the mixed solution for 30min, and then measuring the removal rate of methylene blue.
Step 2. the magnetic porous nanoparticles were recovered and reprocessed from the above mixed solution using the procedure of example 11. And the regenerated particles were put into methylene blue solution (volume same as above) again at a concentration of 80mg/L, and the operation of step 1 was repeated.
As shown in fig. 13, the magnetic porous nanoparticles were continuously subjected to 5 times of removal treatment and regeneration of methylene blue solution of the same concentration, and the removal rate was 99% in each of the 5 times of removal treatment.
In conclusion, the magnetic porous nanoparticles disclosed by the invention are simple and convenient to recover and regenerate, strong in regeneration capacity and high in recycling frequency.
Attached Table 1.Fe3O4Effect of the feed ratio with TEOS on the end product
Figure BDA0002308911120000131
Attached Table 2.DA and Fe3O4Influence of the feed ratio on the end product
Mass ratio of 1∶0.5 1∶0.8 1∶1 1∶1.2 1∶4 1∶1.6 1∶2 2∶1 4∶1
Removal amount mg/g 1500 1600 2500 2600 2500 2600 2400 500 600
Number of times of recycling 4 4 5 4 4 5 5 3 2
TABLE 3 influence of hydrothermal treatment temperature on the final product
Figure BDA0002308911120000132

Claims (10)

1. A magnetic porous nanoparticle, which is characterized by comprising a polydopamine closed shell with a porous structure and any one of the following characteristics:
(1) magnetic particles are arranged in the polydopamine shell and in the pores of the shell;
(2) magnetic particles are arranged in the polydopamine shell;
wherein the aperture of the polydopamine shell in the characteristics is 5 nm-10 nm, and the specific surface area is 190m2/g～210m2The magnetic particles have a particle size of 4 to 6 nm.
2. The nanoparticle of claim 1, wherein voids exist between the magnetic microparticles within the polydopamine shell.
3. The nanoparticle of claim 1, wherein the outer shell of polydopamine has an irregular outer shape.
4. The nanoparticle of claim 1, wherein the nanoparticle is chemically stable at a pH of 2 to 10.
5. A method of making the nanoparticle of claim 1, comprising the steps of:
A1. preparing magnetic particles with the particle size of 4 nm-6 nm;
A2. mixing the magnetic particles prepared in the step A1 with tetraethyl orthosilicate in a mass-to-volume ratio of 1: 1-1: 3 in an alkaline environment to prepare a composite solution;
A3. adding dopamine into the compound solution prepared in the step A3 for reaction;
A4. centrifuging the reaction solution obtained in the step A3, and collecting solid substances;
A5. and D, adding the solid matter collected in the step A4 into HCl-tris buffer solution, carrying out hydrothermal treatment at 140-160 ℃ for not less than 24h, filtering and washing.
6. The method according to claim 3, wherein the ratio of the input volume of dopamine in step A3 to the use volume of magnetic particles in step A2 is 1:1 to 1: 2.
7. A method of using the nanoparticle of claim 1, comprising the steps of:
B1. at a ratio of not more than 1:104Weighing the nano particles according to the mass-volume ratio, and putting the nano particles into a liquid system containing the organic dye;
B2. shaking at normal temperature.
8. A method of regenerating the nanoparticles of claim 1, characterized in that it comprises the following steps:
C1. magnetically enriching the used nanoparticles;
C2. preparing a cleaning solution by adopting absolute ethyl alcohol and deionized water with the same volume;
C3. and C, soaking and washing the nanoparticles collected in the step C1 for multiple times by using the washing liquid prepared in the step C2 until the washing liquid is colorless, and recovering the solid.
9. A material comprising nanoparticles as claimed in any one of claims 1 to 4.
10. Use of a material according to claim 9 for degrading organic dyes.
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